Tetranitrodiethylamine derivatives



United States l atent 2,985,683 TE'I RANTIRODIETHYLAMINE DERIVATIVES Karl Eager, 168 N. Canyon Blvd., Monrovia, Calif.

No Drawing. Filed Jan. 7, 1957, Ser. No. 632,947 16 Claims. (Cl. 260465.5)

(Granted under Title 35, US. Code (1952), sec. 266) The invention described herein may be, manufactured and used by or for the Government of the United States of America for governmental purposes without the payment of any royalties thereon or therefor.

This application is a continuation-in-part of applicants copending application Serial No. 258,977, filed November 29, 1951, for tetranitrodiethylamine Derivatives and Process for Preparing Same, now abandoned.

This invention relates to new tetranitrodiethylamine derivatives and to a process for the preparation thereof. Specifically, these new compoundsma-y be represented by fie following structural. formula:

NO: H R H N:

=- R J- N R N01 111 02 in which R represents a member of the group including hydrogen, halogen, and. alkali metals, and R represents a member of the group including cyano, nitro, and nitroso. It will beunderstood. thatwhen R represents an alkali metal, potassium for. example, that. atom. will be associated with one of thenitro groups adjacent tothe carbon atom rather than with the carbon atom directly. As examples of compounds coming within the scope of the above mentioned formula, there may be mentioned the following: 2,2'-dibromo N-cyano-2,2,2',2'-tetranitrodiethylamine, dipotassium N1nitro-2,2,2', -tetranitrodiethylamine, N-nitroso;2 ,2,2',2'-tetranitrodiethylamine, N-cyano 2 ,2,2,2'-tetranitrodiethylamine, and the like.

An object ofthe invention is to provide new nitro compounds. Another object of the invention is to provide a process for the production of new tetranitrodiethylamines. A further object is to provide a process for reacting tetranitrodiethylamine with other nitrogen containing compounds under moderate, controlled conditions to form N-substituted tetranitrodiethylamines. Further objects will appear hereinafter.

Prior to the instant invention, investigators utilized reactions involving drastic conditions, of temperature and pressure to form various, nitrogen containing aliphatic compounds. lt'has been discovered that dipotassium 2,2,2, -tetranitrodiethylamine reacts readily with certain nitrogen containing compounds in aqueous solution at moderate temperatures and at atmospheric pressure. The yields are nearly quantitative, and'there is very little difficulty with side reactions or in isolating the desired products. 2,2 dibromo 2,2,2',2' tetranitrodiethylamine undergoes reaction with nitric acid to form either the nitroso or the nitro derivative depending upon the concentration of the nitric acid. The cyano derivative formswithsuchease that it is suflicient to employ a salt containing :the cyanoradical for the reaction with tetranitrodiethylamines. The-nitroso member may also be derived fro na salt e.g., sodium nitrite. Temperatures ranging from 0 to 85 C. may conveniently be-employed-in carrying out the reactions.

The 2,2,2, '-tetranitrodiethylamine contemplated by Patented May 23, 1961 H H H NO OK N01 I l 1 10,

It will be evident that the potassium associated with the nitro group may be replaced by hydrogen or halogen attached directly to the adjacent carbon atom without change in the properties of the compound as a secondary amine.

The examples which follow are illustrative of the Van'- ous types of tetranitrodiethylamine derivatives that come within the scope of the invention. They are likewise illustrative of the procedures whereby these new chemical compounds may be synthesized.

Example L-SO gm. of 2,2'-dibromo-2,2,2',2-tetranitrodiethylamine was added in small portions to 300 ml. nitric acid at a temperature of 60 to 65 C. with good agitation. Red brown gases were developed. After 30 minutes of additional stirring at the same temperature, the reaction mixture was heated to 70 C. for a short time. After cooling the mixture to room tem perature, the precipitated N-nitroso-2,2-dibromo-2,2,2,2- tetranitrodiethylamine was collected on a filter and washed: with water until free from nitric acid. The dry material had a melting point of 117 to 11-8 C.

Example II .-3 gm. of 2,2-dibromo-Z,2,2,2' tetrani trodiethylamine was dissolved in 30 ml. sulfuric acid and 1.5 gm. sodium nitrate slowly added with vigorous stir ring. After standing for 4-hours the solution-was mixed with 300ml. icewater. The precipitated white crystals werefiltered off and washed with water. After being twice recrystallized from. isopropyl'ether the material melted at 116 to 11-7 C.' and'was identical with the N- nitroso- 2;2""- dibromo 2,2,2';2' tetranitrodiethylamine obtained by means of the procedure given in Example'l'i Example-'III-.--A suspensionof 9. 16 gm. N'-nitroso'-,2,2- dibromo-Z,2;2',2{-tetranitrodiethylamine in 50 ml. of? methanol cooled to- 0 C. was prepared. A- solution. preparedfrom26 gm. KCN, 15 ml. water and 15 ml. methanol, wasadded dropwise into the suspension while stirring rapidly. The'resulting yellow precipitate ob} tainedwasfiltered andwashedwith methanol.- The yield was 11' gm. of'damp dipotassium salt of N-nitroso-Z ,2,"2" ,2' et an t o thyla e- Example-I V.-8-gm. ofdamp dipotassium N-nitroso- 2,"2,2",2'tetranitrodiethylamine was suspended in 35 ml. water. To this sus'p'ension; ml. dichlorometliane' was added and 1 5fm1;of dilute-sulfuric acid (1 :4 concentrated" acid to water by weightldropped into the mixture while stirringrapidly. 'The;-temperature was kept'at 0C. The yellow saltjdisappeared quickly and the reaction mixturebecame colorless. Afterseparatingthe two layers-in a separatory funnel, the dichloromethane solution was dried over sodiumsulfate'and then evaporated. The remaining yellow oilcrys'tallizfedwhen'cooled' to 70 C. After recrystallization" from dichlorometh'ane, the N-nitroso 2,2,2(,2-tetranitrodiethylamine obtained melted at 6=1 CL withdecompositiom Example V .'A three-necked flask fitted-With a stirren; dropping funnel and thermometer'was charged with 1615 gm.2,2' dibromo-2g2,2',2' tetranitrodiethylamine dissolved in ml." methanol. A=solution prepared from 11 gm; potassiumcyanide dissolved in 22 ml. water and 20ml. methanolwas dropped-into thefiask with eilicient stirring whilekeeping thetempera'ture. of the. reaction mixture at 0- to 109C. Aftervalhthe. potassium cyanide solutions had been. added,.th'e stirring was continued for 50'. minutesia.

The yellow precipitateawas a then filteredofi; 'and washed: with -.met-ha.nol.-r The wield-was 520; gm}. of. .damp; .crude 3 dipotassium N cyano 2,2,2',2 tetranitrodiethylamine. For purification, the salt was suspended in 250 ml. water and brominated at "v to 10 C. until the color of bromine was no longer bleached. After fifteen minutes of additional stirring, the precipitated N-cyano-2,2'-dibromo- 2,2,2',2'-tetranitrodiethylamine was filtered off, washed with water, dried, and recrystallized from chloroform. The yield was 9.1 gm. of substantially pure compound having a melting point of 157 to 158 C.

Example VI.-A three-necked flask provided with a stirrer, dropping funnel and thermometer was charged with 130 ml. methanol and 13.1 gm. N-cyano-2,2'-di bromo-2,2,2,2'-tetranitrodiethylamine. A solution prepared from 4.3 gm. potassium cyanide, 10ml. water and 10 ml. methanol was dropped into the suspension in the flask while keeping the reaction mixture at a temperature of 0 to 10 C. After stirring for an additional fifteen minutes, the yellow dipotassium salt of N-cyano-2,2,2',2'- tetranitrodiethylamine was filtered off and washed with methanol.

Example VII.-Three gm. of dipotassium N-cyano- 2,2,2,-2'-tetranitrodiethylarnine was suspended in 75 ml. water and acidified with 20% sulfuric acid. The yellow precipitate disappeared and a white precipitate was formed. After filtration and Washing with water until free from acid, the white crystals of N-cyano-2,-2,2',2'-tetranitrodiethylamine were dried. The melting point was 88 C. with decomposition.

Example VIII.-5 gm. of 2,2'-dibromo-2,2,2',2'-tetra nitrodiethylamine was introduced in small quantities into 50 ml. fuming nitric acid at a temperature of 60 C. Red brown gases were evolved. After all material was added, the mixture was stirred for 30 minutes at 65 to 70 C. A white precipitate was formed. After cooling to room temperature, the N-nitro-2,2-dibromo-2,2,2',-2'-tetranitrodiethylamine was filtered ofl and washed with 70% nitric acid and water. The melting point of the compound was 165 to 167 C. with decomposition.

Example IX .--A suspension of 7.6 gm. N-nitro-2,2'-dibromo-2,2,2,2'-tetranitrodiethylamine in 75 ml. methanol was prepared and cooled to 0 C. A solution of 15 gm. potassium iodide in 15 ml. water and 15 ml. methanol was added dropwise to the suspension while stirring rapidly. Free iodine was formed and a yellow precipitate appeared. After 30 minutes of additional stirring, the resulting dipotassium salt of N-nitro-2,2,2,2'-tetranitrodiethylamine was filtered off and washed with methanol until free from iodine. The yield was 93.7% of theoretical.

Example X.-1 gm. of dipotassium N-nitro-2,2,2',2'- tetranitrodiethylamine was suspended in ml. water, and dilute sulfuric acid (1:4 acid to water by volume) was added until the yellow color disappeared. A white crystalline precipitate was formed. After filtration and washing with ether, the N-nitro-2,2,2',2'-tetranitrodiethylamine was dried in a desiccator. The yield was 0.4 gm. of the compound which had a melting point of 78 C. with decomposition. l a

The highly nitrated compounds resulting from the above described process are valuable explosives intermediates since they have a favorable oxygen balance, are relatively stable, form uniform crystals, and are smokeless.

The compounds of this invention are useful as high explosives and can be used in any conventional explosive missile, projectile, rocket, or the like, as the main explosive charge. An example of such a missile is disclosed in United States Patent No. 2,470,162, issued May 17, 1949. One. way of using the high explosives of this invention in a device such as that disclosed in United States Patent No. 2,470,162, is to pack'the crystalline explosive in powder form into the warhead of the missile. Alternatively, the crystals can be first pelletiaed and then packed. A charge thus prepared is sufficiently insensitive to withstand the shock entailed in the ejection of a shell' from a gun barrel or from a rocket launching tube under aesaees the pressure developed from ignition of a propellant charge, and can be caused to explode on operation of an impact or time fuse-mechanism firing a detonating explosive such as lead azide or mercury fulminate.

Obviously many modifications and variations of the present invention are possible in the light of the above teachings. It is therefore to be understood that within the scope of the appended claims the invention may be practiced otherwise than as specifically described.

What is claimed is:

l. Tetranitrodiethylamines having the formula:

N0, H R H No,

7. N-nitro-2,2-dibromo-2,2,2',2'-tetranitrodiethylamine 8. The method of preparing tetranitrodiethylamine co positions having the structural formula: NO: H R: NO: R ---ING R1 NO: H N0:

wherein R is a member selected from the group consisting of chlorine, bromine and fluorine, and R is a member selected from the group consisting of nitroso, cyano and nitro, which comprises reacting a tetranitrodiethylamine composition having the structural formula:

wherein R is a member selected from the group consisting of chlorine, bromine and fluorine, with a reactant selected from the group consisting of dilute nitric acid, a mixture of sulfuric acid and sodium nitrate, concentrated nitric acid, and an aqueous solution of potassium cyanide.

9. The method of preparing tetranitrodiethylamine compositions having the structural formula:

wherein R is a member selected from the group consisting of nitro, nitroso and cyano, which comprises reacting a salt having the structural formula:

1700K H R: H NOOK i i 1 N01 H NO:

wherein R is a member selected from the group consisting of nitro, nitroso and cyano, with dilute acid.

assaess 12. The method of preparing N-nitro-2,2-dibromo- 2,2,2,2'-tetranitrodiethylamine which comprises reacting 2,2'-dibromo-2,2,2',2'-tetranitrodiethylamine with fuming nitric acid.

13. The method of preparing N-cyano-2,2,2',2'-tetranitrodiethylamine which comprises reacting 2,2'-dibromo- 2,2,2,2'-tetranitrodiethy1amine with an aqueous solution of potassium cyanide to form dipotassium N-cyano-2,2, 2',2'-tetranitrodiethylamine and thereafter neutralizing the said dipotassium salt with bromine in aqueous solution.

14. The method of preparing N-nitroso-2,2,2,2'-tetranitrodiethylamine which comprises reacting dipotassium N-nitroso-2,2,2',2-tetranitrodiethylamine with dilute sulfuric acid.

15. The method of preparing N-nitro-2,2,2',2-tetranitrodiethylamine which comprises reacting dipotassiurn N- 6 nitro-2,2,2',2'-tetranitrodiethylamine with dilute sulfuric acid.

16. The method of preparing N-cyano-Z,2,2',2'-tetranitrodiethylamine which comprises reacting dipotassium N- cyano-2,2,2',2'-tetranitrodiethylamine with dilute sulfuric acid.

References Cited in the file of this patent Degering: An Outline Organic Nitrogen Compounds (1945), page 213. 

1. TETRANITRODIETHYLAMINES HAVING THE FORMULA: 